Dyeing and printing on polyamide fibers



United States Patent US. Cl. 8-74 12 Claims ABSTRACT OF THE DISCLOSUREIn the process of dyeing and printing polyamide fibers with reactivedyestuffs, there is provided an after-treatment of the dyed fibers forthe purpose of fixing still unreacted residual dyestulf on the fibers,which after-treatment does not injure the fibers and permits the dryingof the after-treated fibers directly without further intermediatetreatments.

This application is a continuation of application Ser. No. 515,774,filed Oct. 22, 1965, and abandoned since the filing of the instantapplication, which application is in turn a division of application Ser.No. 296,392, filed July 19, 1963, and now abandoned.

This invention relates to improvements in dyeing and printing onpolyamide fibers as well as, as industrial products, the dyed andprinted polyamide fibers treated according to the invention.

Hitherto, wool and other polyamide fibers including nylon and the likesynthetic polyamide fibers which had been dyed with reactive dyestuffscontaining per molecule at least one substituent which can be split offas an anion during the dyeing and/or after treatment of the dyed fibers,had to be subjected to an after-treatment in an aqueous basic medium ofa pH of preferably about 7.5 or higher which contains, for example,sodium hydroxide, sodium carbonate, or preferably ammonia orhexamethylenetetramine as the basic agent.

This known alkaline after-treatment, which serves to fix on the fibersstill unreacted reactive dyestuff present in the dyed goods, suffersfrom the drawback that the polyamide fibers can be injured by thealkaline medium and particularly by a subsequent drying step if the sameis carried out directly on the after-treatment fibers.

Therefore, in the known dyeing methods, the after-treatment with analkaline medium is followed usually by a further treatment in an acidmedium prior to final drying of the dyed or printed fibers.

Another drawback of the after-treatment with alkaline agents such asammonia or hexamethylenetetramine resides in the tendency of thealkaline bath to remove at least part of the still unreacted dyestufffrom the fibers, whereby an exact control of the shade of the fixeddyeing or prints is made very difiicult.

It is, therefore, an object of the present invention to provide, in aprocess of dyeing or printing polyamide fibers with reactive dyestuffsof the type described, as after-treatment of the dyed fibers for thepurpose of fixing still unreacted residual dyestuff on the fibers, whichafter-treatment does not injure the fibers, permits of drying theaftertreated fibers directly without further intermediate treatments,and allows for a more exact control in producing a desired shade.

Patented Sept. 16, 1969 These objects are attained by the treatmentaccording to the invention, which comprises, as an after-treatment indyeing and printing processes for producing colored polyamide fibers byheating and thereby reacting said fibers together with reactive dyestuffwhich contains at least one mobile substituent capable of being splitoff as anion, in an aqueous acid medium, preferably at a pH of about 4.5to 5, and, preferably, with subsequent rinsing of the colored fibers inwater of a temperature of about 10 to preferably 60, and not more thanC., and drying,

(I) Introducing the freshly colored, and preferably immediatelysubsequently rinsed, fibers, directly thereafter and prior to drying,into an aqueous solution of a condensation product of (a) A naphthalenesulfonic acid, in particular a monoto trisulfonic acid, and preferablynaphtha1ene-2-rnonosulfonic acid, or a 1,2,3,4-tetrahydronaphthalenesulfonic acid,

(b) From about 0.5 to 1.5, and preferably from 0.8 to 1.2 parts byweight, per part by weight of (a), of a compound of the formulaHO-phenylene-SO -phenyIene-OH, preferably 4,4-dihydroxy-diphenylsulfone,and

(c) From about 0.1 to 0.2, and preferably 0.1 part by weight, per partby weight of (a), of formaldehyde, in aqueous, preferably about30%-solution.

(II) If necessary, adjusting the pH of the aqueous solution to about 4to 5.5, and preferably to 4.5 to 5, by the addition of acid, such asacetic or formic acid, and preferably of acetic acid, and

(III) Heating the said aqueous solution and the colored fibers thereinfor a short time, about 10 to 60, and preferably 15 to 30 minutes, at atemperature of about 20 to 100, and preferably 60 to C.

According to another mode of carrying out the treatment according to theinvention is practice, the condensation product used as the fixing agentin the aqueous acid solution of steps (I) to (III) described supra, isproduced by condensation of (a) a 0:,w-di0hl010- or a,w-dibromoalkane offrom 2 to 7 carbon atoms, or w,w'-dichloro-dialkylether with a total offrom 4 to 8 carbon atoms, with (b) a tertiary saturated aliphatic aminewith a total of from 6 to 24 carbon atoms and from two to four aminonitrogen atoms, in such molar ratio of (a):(b) that approximately onehalogen atom is present in the condensation reaction for every aminonitrogen atom.

According to yet another mode of carrying out the treatment according tothe invention in practice, there is used in the aqueous solution ofsteps I to III supra, in lieu of the above-mentioned condensationproducts, a product produced by the condensation of (a) Dicyanodiamide,(b) At least one mole, per mole of (a), or an excess thereover, of anammonia donator which is either urea or an ammonium salt of a mineralacid capable of splitting off ammonia, and (0) At least two moles, permole of (a), or an excess thereover, of formaldehyde in aqueous,preferably 30% by weight, solution. A concentration of about 0.5 gram ofcondensation product per liter of solution is the minimum.

In the second and third modes of the treatment according to theinvention described above, the addition of acid to the solution inaccordance with step II, supra, is mandatory.

As polyamide fibers, those of natural origin, above all wool and silk,but also synthetic polyamide fibers such as the various kinds of nylone.g. nylon 6, nylon 66, and nylon 11 (Rilsan), are suitable for theafter-treatment according to the invention.

These polyamide fibers are dyed by known methods in a dyestuif solutionwhich, in addition to the dyestuffs mentioned, can also contain theauxiliaries usual in woo-l dyeing, e.g. salts such as sodium sulfate orammonium sulfate and/or dilute acids, e.g. acetic or formic acid, and/or wetting agents, e.g. condensation products of fatty acids having atleast 8 carbon atoms and lower alkanolamines such as are described inUS. Patent 2,089,212.

The aforesaid fibers are printed by known processes in neutral or acidmedium in the presence of thickeners and, optionally, urea.

The after-treatment according to the invention with the solution of thecondensation products is preferably performed in a solution whichcontains these products in a concentration of about 0.5 to 3 g. perliter, furthermore, optionally, other additives usual in textile dyeing,and

finally, acid, e.g. acetic or formic acid, as mentionedabove.

The aforesaid condensation products suitable for use in the firstabove-described mode of carrying out the invention in practice areproduced as described in German Patent 611,671, issued April 5, 1935;those suitable for use in the second mode of practicing the inventiondescribed above, are produced as described in German Patent 894,237,issued October 22, 1953. This class of condensation products is obtainedby reacting the components mentioned above at a raised temperature,about 50 to 140 C., possibly in the presence of diluents, e.g. butylalcohol, ethylene glycol or diethylene glycol. Among the saturatedaliphatic tertiary polyamines defined above, there are:

Di-, triand tetra-amines such as N .N-tetramethylhexamethylenediamineand homologues, N,N',N"-pentamethyl-di-ethylenetriamine,N,N',N",N'-hexamethyl-triethylenetetramine as well as industrialmixtures thereof also.

Examples of :,w-dih21l0g6n alkanes are 1,2-dichloroor1,2-dibromo-ethane, 1,3-dichloro-propane, 1,4dichlorobutane,1,5-dichloropentane, 1,6-dichlorohexane; w,w-di halogen ethers are,e.g., ,8,B-dichlorodiethyl ether, ethylene glycol-di-B-chloroethylether, p,e-di-(2-ch1oroethoxy)-di-ethyl ether, 'y,y-dichloropropyl etheras well as glycerin dichlorohydrin. The reaction products are mosteffective when the ratio of the reaction components is so chosen thatthere is about one halogen atom per N atom, so that, for example, onusing a triamine, two mols of amine are quaternized with three mols ofa,w-dihalogen alkane. Particularly good results are obtained with thecondensation product of 2 mols of N,N,N"-pentamethy1- diethylenetriamineand 3 mols of fi,/3-dichlorodiethyl ether.

The condensation products usable in the third mode of carrying out thetreatment according to the invention are produced from dicyanodiamideand the ammonium salt of a strong mineral acid or urea, andformaldehyde, as described in German Patent 929,642 issued Oct. 22,1953. Best results are obtained with compounds from this class which areproduced in accordance with Example 2 of German Patent 929,642.

The reactive dyestuffs used according to the invention can be of themost varied classes of dyestuffs. Preferably they are nitro, azo,anthraquinone or phthalocyanine dyestuffs, which classes excel instability. They contain watersolubilizing, acid, salt-forming groups,mainly sulfonic acid groups, possibly also carboxyl groups or sulfamylgroups, in the latter case, among others, also acylated sulfamyl groups,e.g. disulfimide and carbonyl sulfimide groups.

The advantages attained according to the invention are particularlyimpressive when the reactive dyestufis conventionally used for the fastdyeing of cellulose are used which contain sulfonic acid groups, e.g. 2to 4, per dyestuff molecule. Thus, examples of dyestuffs, dyeings ofwhich are especially suitable for use in the treatment according to theinvention are nitrodiarylamine sulfonic acids, metal-free monoandpoly-azo dyestuffs, heavy metal-containing, e.g. chromium orcobalt-containing, o,o'-dihydroxy-, o-hydroxy-o-carboxyando-hydroxyo'-amino-mono-azo and dis-azo dyestufi s, copper-containingformazane dyestuffs, l-amino-4-phenylamino anthraquinone dyestuffs, andcopper phthalocyanines with substituted sulfamyl groups, all of whichpreferably contain at least two sulfonic acid groups.

Mobile substituents which can be split ofli as anion are mainly:radicals of strong acids, in particular halogen atoms, of thesepreferably chlorine, or bromine or fluorine, the mobility of which isdue, for example, to the bond at fi-carbon atoms in negativelysubstituted organic radicals, at S0 groups in the case of fluorine, atcarbon atoms adjacent to teritary ring nitrogen in nitrogen heterocyclesof aromatic character, in this case preferably 6-membered heterocycleshaving at least two tertiary ring nitrogen atoms; aromatically boundhalogen atoms in oand/or p-position to one (or more) electrophilicgronp(s), in particular fluorine or chlorine atoms; further, forexample, the radical of sulfuric acid in sulfated fl-hydroxyalkylcompounds, e.g. in sulfated ,B-hydroxy-alkyl sulfonyl and sulfamylgroups; or the radical of hydroxyaryl compounds in O-aryl urethanegroups.

Dyestuffs usable according to the invention contain the substituentwhich can be split off as anion, for example, in the form of fl-chloroorfl-bromo-fatty acid amide groups, in which case fl-chlorocrotonic acidamide or fl-bromopropionic acid amide groups are preferred; or the saidsubstituent is in the form of fluoroor chloronitrobenzoylamino groups orfluoroor chloro-nitrobenzene sulfonylamino groups in which the fluorineor chlorine atoms are in the oand/or p-position to the nitro groups orgroups; or, preferably, it is in the form of chloroorbromo-diazinylamino triazinylamino groups, in which case it is inparticular in the form of monochloroor dichloro-s-triazinylamino groups,and preferably, dior tri-chloropyrimidylamino groups. Dyestuffs with atleast one dior tri-halogen pyrimidylamino group and at least 2 sulfonicacid groups are preferred in the dyeing and printing processescomprising the after-treatment according to the invention.

An advantage of the treatment according to the invention over the knownprocesses is the elimination of an alkaline aftertreatment with, forexample ammonia or hexamethylenetetramine. This advantage becomes mostapparent in the dyeing and printing of wool which is sensitive toalkali, as the danger of injury to the fibers inherent in the alkalineafter-treatment is avoided.

Moreover, the control of producing the desired shade more exactly isfacilitated since changes in shade due to shifting of the pH of thedyeing medium from acid to alkaline and possibly back to acid areavoided.

Dyeings or prints on polyamide fibers attained according to theinvention are distinguished by pure, strong and even shades and goodfastness properties. In particular, they have remarkable wet fastnessproperties, for example fastness to water, washing, milling andperspiration, and particularly to sea-water.

The following non-limitative examples illustrate the invention. Wherenot otherwise stated, parts and percentages are given by weight. Therelationship of parts by weight to parts by volume is as that of gramsto cubic centimeters. The temperatures are given in degrees centigrade.

Example 1 parts of wool are dyed in 4000 parts of a dye liquor whichcontains the following agents:

4 parts of a dyestuif of the formula ('31 (El C-C s 17111-0 /N N=C-N=N-- S0311 HOsS SO3H 0.5 part of a condensation product of 1 mol ofoleic acid and 2 mols of diethanolamine (Example 5 of US. Patent No.2,089,212),and

4 parts of 80% acetic acid.

The goods are introduced into the liquor at 50, dyeing is performed forminutes at this temperature, the bath is brought to the boil withinminutes and dyeing is continued at the boil for minutes.

After dyeing, the goods are well rinsed and treated in a fresh bath for20 minutes at -80 which contains 0.75 g. per liter of a condensationproduct of formaldehyde with dihydroxydiphenyl sulfone and naphthalenesulfonic acids, the production .of which condensation product isdescribed below, as well as 0.25 g. per liter of acetic acid.

Valuable red dyeings are obtained in this way which are very wet fast.

The condensation product mentioned is obtained as follows:

parts of the sulfonating mixture, obtained by heating for several hoursat -160", 520 parts of naphthalene and 5 60 parts of concentratedsulfuric acid until water solubility is attained, are heated for about 1hour at 105110 with 100 parts of a dihydroxydiphenyl sulfone, 50 partsof water and 45 parts of formaldehyde (30%). The dihydroxydiphenylsulfone is obtained by heating 540 parts of phenol and 180 parts of 60%oleum for 3 hours at -180 and distilling 01f excess phenol.

By using, instead of the dyestufl? given in Example 1, the dyestuffslisted in column 2 of the following table, and otherwise following theprocedure described in said example, wool dyeings of the shade given incolumn 3 and of good fastness to washing, perspiration and sea water areobtained.

TABLE I No. Dyestufi Shade on wool 1 CH Greenish-yellow.

o1 SOH 3 a I c N:

L 11038 NH-C (J H a 1 CH C] 2 n Reddish-yellow.

l l N=N-C NH-i1 o o1 CH3 3 (31 Red.

N N H A i k N 01 N=N SOaH SO;H 80 11 4 1TH; Blue.

SOaH

b NH-Qsom son! Cl S 03150 Scarlet.

N-O SOsH NH-C N TABLE 1Contlnued No. Dyestuff Shade on wool 13.. HoNlEllz Blue-black.

HOaS-OCH2CH2S Oz-N= N=NC S 0zCH2CH2O-SOaH H035 -S0aH 14..." /Ol Blue.

HOHS c Cu(|) lTIH-O N I N=C NH- -S0:H

' HO S- SO H Example 2 Example 4 W001 is printed with a printing pasteof the following Nylon is printed with a printing paste of the followingcomposition: composition:

30 parts of the dyestutf of the formula parts of the dyestutf of theformula 01 e1 CH3 C1 JJJJ so H 3 HO NH--O N I I 1103s NH- .'-o1

01 l 0 SOaH 11033 $0311 50 parts f urea 250 parts of boiling water, 100parts of urea, 5 p r s f phenol, 10 parts of the sodium salt ofm-nitrobenzene sulfomc 30 parts of throdiethylene glycol, acid 450 partsof 5% sodium alginate solution, and

450 parts of 5% sodium alginate solution, and 1 5 parts of water. 410parts of water. The goods are then dried and steamed and rinsed, firstThe goods are then dried, steamed and well rinsed with 4 w1th cold andthen with 60 warm water.

cold water.

The rinsed wool is then treated for 20 minutes at 60- 80 in a fresh bathwhich contains 0.75 g. per liter of theformaldehyde/dihydroxydiphenylsulfone/naphthalene sulfonic acidscondensation product used in Example 1, supra, as well as 0.5 g. perliter of aqueous 80% acetic acid.

In this way, valuable red prints are obtained which have very good wetfastness properties.

Example 3 and 1 part of 80% acetic acid.

The goods are entered into the liquor at 40, dyeing is performed for 10minutes at this temperature, the bath is brought to the boil within 30minutes and dyeing is continued for minutes at the boil.

After dyeing, the goods are well rinsed and treated for 20 minutes at6080 in a fresh bath which contains 0.75 g. per liter of theformaldehyde/dihydroxydiphenylsulfone/naphthalene sulfonic acidscondensation product mentioned in paragraph 3 of Example 1 and 0.25 g.per liter of 80% acetic acid.

In this way, valuable greenish yellow dyeings which have very good wetfastness properties are obtained.

The rinsed goods are after-treated in a fresh bath in the mannerdescribed in the previous Example 3.

In this way, valuable greenish yellow prints are obtained, which havevery good wet fastness properties.

Example 5 100 parts of wool are dyed in 4000 parts of a dye liquor whichcontains the following agents:

4 parts of a dyestutf of the formula no NH--C/ 1 N N N=o soar: HOaS-S0311 0.5 part of a condensation product of 1 mol of oleic acid and 2mols of diethanolamine (Example 5 of US. Patent No. 2,089,212) and t 4parts of acetic acid.

These goods are introduced at dyeing is performed for 10 minutes at thistemperature, the bath is brought to the boil within 10 minutes anddyeing is performed at the boil for 45 minutes.

After dyeing, the dyed goods are rinsed and treated for 1 mentioned, anitrogen-containing condensation product of 34 parts of dicyanodiamidewith 5.5 parts of ammonium chloride, 18 parts of urea and 80 partsformaldehyde is used in the after-treatment liquor and otherwise thesame procedure is followed.

If, instead of the dyestuff mentioned in the example, those given incolumn 2 of the following table are used and otherwise the proceduredescribed in the example is followed, then corresponding wool dyeings asgiven in 5 column 3 are obtained.

TABLE II No. Dyestufi Shade on wool 1 (I311: 1 Greenish-yellow.

HO S

N N N H I HOaS-- NH-C C 0 01 H Cl 2 (I31 Reddish-yellow.

C SlOaH II N=N- -NHC\ o Cl CHa 3 (31 Red.

ll 5 HO NH-C C "SOZH S0311 $0311 4 (H) IIIHz Blue.

SOQH

S|O H -fi I G N N i 01 5..-... (IHI $10 11 Scarlet;

C1 SO3H SOSH I NH-C N i 9 C1 C1 6 (|)II NH-OO-CH=CCH Orange.

SOJH SOaH 7...... C1 C1 Turquoise blue.

(HSO;);-{Cu-1hto.}SOz-NH- I) NH--C\ /N (wherein CuPhto. is the copperphthaloeyaniue radical) 15 Example 6 W001 is printed with a printingpaste of the following composition:

30 parts of the dyestuff of the formula 31 Cl HO NHC N SOaH H 8 $0311100 parts of urea,

110 parts of the sodium salt of m-nitrobenzene sulfonic acr 450 parts of5% sodium alginate solution, and

410 parts of water.

The goods are then dried, steamed and well rinsed with cold water.

The rinsed wool is after-treated as described in Example 1. In this way,valuable, vivid bluish red prints are obtained which have very good wetfasteness properties.

Similar results are obtained if, instead of the reaction products asdescribed in Example 1, a nitrogen-containing condensation product of 34parts of dicyanodiamide with 12 parts of ammonium chloride, 12 partsurea and 80 parts of formaldehyde are used.

Example 7 100 parts of nylon are dyed in 4000 parts of a dye liquorwhich contains 1.5 parts of a dyestufi of the formula and 1 part of 80%acetic acid.

The goods are introduced at 40, dyeing is performed for 10 minutes atthis temperature, the bath is brought to the boil within minutes anddyeing is continued for minutes at boiling temperature.

After dyeing, the goods are well rinsed and then treated in a fresh bathfor 20 minutes at 80 which contains 0.75 g. per liter of the reactionproduct of 2 mols of N,N,N"-pentamethyl diethylene-triamine and 3 molsof p,f3'-dichlorodiethyl ether, and also 0.5 g. per liter of 40% aceticacid. In this way, valuable greenish yellow dyeing which have very goodwet fastness properties are obtained.

Similarly good dyeings are obtained if, in the above example, anitrogen-containing condensation product of 34 parts of dicyanodiamidewith 11 parts of ammonium chloride, 12 parts of urea and 80 parts offormaldehyde is used in the after-treatment bath instead of the reactionproduct mentioned and otherwise the same procedure is followed.

Example 8 Nylon is printed with a printing paste of the followingcomposition:

@ HOS NHE 50 parts of urea,

250 parts of boiling water,

45 parts of phenol,

30 parts of thiodiethylene glycol,

450 parts of 5% sodium alginate solution and 145 parts of water.

The goods are then dried, steamed and rinsed first with cold and thenwith 60 warm water.

The rinsed goods are after-treated as described in Example 3. In thisway, valuable greenish yellow prints which have very good wet fastnessproperties are obtained.

Similar results are further obtained if, instead of the reaction productas described in Example 3, a reaction product obtained fromcorresponding amounts of N,N- tetramethyl ethylene diamine and'y,'y-dichloropropylether or 1,4-dibromobutane or corresponding amountsof N,N tetramethyl tetramethylene-diamine and glycoldichlorohydrin isused.

We claim:

1. In dyeing and printing processes for producing colored polyarnidefibers by heating and thereby reacting said fibers together withreactive dyestutf which contains at least one mobile substituent capableof being split off as anion, in an aqueous acid medium, and then dryingthe colored fibers, the improvement comprising (1) introducing polyamidefibers freshly colored with reactive dyestuff, after coloration andprior to drying, into an aqueous solution of a condensation product of(a) a member selected from the group consisting of a naphthalenesulfonic acid and a 1,2,3,4- tetrahydronaphthalene sulfonic acid, (b)from about 0.5 to 1.5 parts by weight of a compound of the formulaHO-phenylene-SO -phenylene-OH per part by weight of (a), and

(c) from about 0.1 to 0.2 part by weight of formaldehyde per part byweight of (a), in aqueous solution,

(H) adjusting the pH of the aqueous solution to about 4 to 5.5 by theaddition of acid, and

(III) heating the said aqueous solution and the colored fibers thereinfor about 10 to 60 minutes at a temperature of about 20 to 100 C.

2. The improvement described in claim 1, wherein the member (a) is anaphthalene-monosulfonic acid.

3. The improvement described in claim 1, wherein the member (a) isnaphthalene-Z-sulfonic acid.

4. The improvement described in claim 1, wherein the compound under (b)is 4,4-dihydro-diphenylsulfone.

5. The improvement described in claim 1, wherein the compound under (b)enters into the condensation product at a ratio of 0.8 to 1.2 part byweight per part by weight of (a).

6. The improvement described in claim 1, wherein the heating under stepHI is carried out for about 15 to 30 minutes.

' 7. The improvement described in claim 1, wherein the aqueous acidsolution and fibers therein are heated in step III at a temperature ofabout 60 to C.

8. The improvement described in claim 1, wherein the acid added in stepII is a member selected from the group consisting of acetic acid andformic acid.

9. The improvement described in claim 1, wherein, in step II, the pH isadjusted to about 4.5 to 5.

17 18 10. The improvement described in claim 1, further References Citedcomprising the step of rinsing the colored fibers, after UNITED STATESPATENTS removal from the dyeing medium and prior to introduction intothe aqueous solution containing the condensa- $298,774 1/1967 Solron eta1 874 2,623,806 12/1952 Fuchs 821 tion product, with water having atemperature of about 5 10 to 70 C., but not higher.

11. The im rovement described in claim 1, wherein said reactivedfiestuff contains a halogen-substituted pyrim- GEORGE LESMES PnmaryExammel' idylamino reactive dyestuff radical and from 2 t0 3 sul- T. J.HERBERT, JR., Assistant Examiner fonic acid groups. 10

12. The improvement described in claim 1, wherein U.S. C1.X.R. saidpolyamide fibers are wool. 85 4, 55

3,118,723 1/1964 Harding.

